Process for color developing, including treatment with a quaternary ammonium salt



Patented May 1, 1951 2,551,091 ICE PROCESS FOR COLOR DEVELOPING, IN- CLUDING TREATMENT WITH A QUA- TERNARY AMMONIUM SALT Vernon William Blanchard, South River, N. J.,

assignor to E. I. du Pont de Nemours and Company, Wilmington, DeL, a corporation of Delaware No Drawing. Application September 14, 1949, Serial No. 115,769

6Claims. 1

This invention relates to processes of color photography. More particularly it relates to a process for modifying the color of quinoneimine and/or azomethine dye images obtained from the color coupling development of immobile color formers containing a sulfonamide or carbonamide group having a hydrogen atom attached to the amino-nitrogen atom in photographic elements. Still more particularly it relates to a process of treating an exposed photographic element which contains an immobile color former containing a carbonamide or sulfonamide group having a hydrogen atom attached to the amidenitrogen atom after exposure but prior to completion of aqueous processing. Still more particularly it relates to such processes wherein a surface-active quaternary ammonium compound is used in the aqueous treating bath.

An object of this invention is to improve the color of the quinoneimine or azomethine dye image or images obtained from color formers of the above type which are disposed in a layer of a photographic element. A further object is to provide a simple and economical but yet effective method of varying the color of such quinoneimine or azomethine dye images. Still other objects will be apparent from the following description of the invention.

It has been found that the color of a quinoneimine or azomethine dye image formed by the color coupling development of a colloid silver halide emulsion layer group photographic element can be modified by treating an element which contains or contained an immobile color former containing a carbonamide or sulfonamide group having a hydrogen atom attached to the amido-nitrogen atom disposed in, or constituting a water-permeable colloid layer, after exposure, in an aqueous treating solution containing a small amount of a surface-active quaternary ammonium salt having an aliphatic hydrocarbon radical of 8 to 22 carbon atoms attached to the pentavalent nitrogen atom.

The aqueous treating solution containing such salts may be applied at any stage in the pro-cessing of the exposed film to a dye image e. g., prior to, during or subsequent to development. The salts are preferably used in the aqueous alkaline developer solution. The amount of quaternary ammonium salt used in the aqueous treating bath can be varied over a fairly wide range, but in general, from 0.2 gram to 25 grams per liter of solution is sufficient to make a significant change in the color of the dye image.

While the invention is useful with any immobile color former containing a primary carbonamide group or a primary sulfonamide group it is especially useful with color former amidobenzaldehyde acetals of hydroxyl polymers containmg a plurality of recurring intralinear groups. The color former units of the polymer may be represented by the formula:

I o-tn RXN on tn,

wherein the free bonds are attached to the other chain units e. g.,

groups. R is a color former nucleus which is oined directly to X or through a hydrocarbon radicaLXis or -SO2. R. may be a py azolone, phenol, naphthol or acylacet nucleus. A relatively large number of such color formers are known to the art. Some are described in U. S. Patents 2,310,943, 2,320,422, 2,380,032, 2,380,033, 2,397,864, 2,423,572, 2,464,597, 2,465,067. Still others are described in assignees copending applications Serial Nos. 9,330, filed February 18, 1948, now Patent No. 2,513,190 and 19,155, filed April 5, 1948, now Patent No. 2,489,655.

It has been found, for example, that the magenta azomethine dyes which are formed from a polyvinyl acetal color former containing the following color former nuclei which are attached to a polyvinyl alcohol chain by an acetal linkage are especially beneficially improved in color by the foregoing treatment:

CHa- J Hz z i (I) scum-Q 5 Ill oHs-tttm 11)" The color change consists in a narrowing and shifting of the green absorption band and an increase in the red and blue transmission. The

can

on OH ooNH o11 (tn, o-+11 on2 As previously stated, it is preferred to have the quaternary ammonium salts in the color developer solutions. The latter solutions may be any of the conventional types and contain a color developing agent having an unsubstituted amino (NH2) group such as phenylene diamine and its N-monoalkyl and N-dialkyl substitution products containing from 1 to 4 carbon atoms in the alkyl group of which p-diethylaminoaniline is the preferred agent. These color developing agents are usually used in the form of their water-soluble salts since the latter are more stable and are more easily dissolved. Suitable salts are the hydrochloride, sulphate and chloracetate. The developer solutions moreover, may contain the usual water-soluble sulfites, e. g., sodium, potassium, and ammonium sulfite and alkalies, e. g., sodium carbonate, ammonium hydroxide and sodium metaborate and other developer constituents.

The invention will be further illustrated but is not intended to be limited by the following examples wherein the parts stated are by weight unless otherwise indicated.

Example I A cellulose acetate film base bearing a layer composed of light sensitive silver salts dispersed in a polyvinylacetal containing color former units of Formula II above was exposed and developed for 10 minutes at 68 F. in a solution made by admixing the following ingredients:

The film was washed in water for 2 minutes, fixed at 68 F. for minutes in a solution made by adding 200 grams of desiccated sodium hyposulfite in one liter of water, washed minutes,

bleached 5 minutes in a bath of the formula:

K3Fe(CN)s grams 60 Boric acid do 10 Borax do 5 Water to liter 1 washed 2 minutes, fixed 5 minutes in a solution made by admixing the following ingredients:

Ammonium thiocyanate grams 100 Borax do 50 Water to liter 1 washed in water for 15 minutes and dried. A strip of the film was then soaked for 5 minutes in a 0.1% aqueous solution of a mixture of long chain alkyl trimethyl ammonium bromide wherein the alkyl groups contained from 8 to 18 carbon atoms and correspond to such groups in the higher alcohols obtained from the hydrogenation of cocoanut oil. The color of the dye image obtained was markedly changed as compared with a second strip of the film which was not given the latter treatment, there being a shift in the green absorption band and an increase in the red and blue transmission.

A third strip was soaked in a similar bath containing, in addition to the surface active ammonium salts, 3% of sodium carbonate. The color change was similar to the first strip.

Upon soaking the first. and third strips in an aqueous solution. containing 0.5% of a mixture of alkyl sulfates of 10 to 13 carbon atoms the color changed back to approximately the color of the second strip.

Example II A photographic film element bearing a layer composed of light-sensitive silver salts dispersed in the polyvinyl acetal color former of Formula I above was exposed to an object field and then processed as follows:

1. Developed for ten minutes at 68 F. in a color developing solution made by admixing the following components:

p-Aminodiethyl aniline-H01 grams 2.50 NazSOz (desiccated) do 10.00 NaZCO'S'HZO do 29.25 K'Br do 2.00 Ctyl pyridinium bromide (A) ;do 5.00 Water to liter 1 2. Washed in water for three minutes; 3. Fixed at 68 F. for ten minutes in a solu tion made by admixing the following ingredients:

Sodium thiosulfate "grams" 200 Water to liter 1 4. Washed in water for 15 minutes;

5. Bleached for five minutes at 68 F. in a solution made by admixing the following in gredients:

IQFe(CN)e grams 60 Boric acid do 10 Borax do 5 Water to liter 1 6. Washed for two minutes in water; 7. Fixed for five minutes at 68 F. in a solu tion made by admixing the following ingredients:

Ammonium thiocyanate grams 100 Borax do 50 Water to liter 1 8. Washed for a period of 15 minutes in water and dried.

' In the above procedure, a control film was treated in exactly the same way except that the cetyl pyridinium bromide was omitted from the er. diisoiautyli phenoxytime ethyl; dimetthyli benzyl ammonium; chloride (25. aqueous; 50.3111.- tio'rr) (Db-,and 5.1.0.0. per liter of. the; cluaternar-y ammoniumisaltz aqueous solution) of Example: I; (E). with the results; given in: the foil:- lowing table; ascompared? with control films not 6', monium-ibromides octadeor itmmethrlz iodide, cetyl i ylr ammorfium: iodidei. cetr triethyl ammonium iodide, cetyl trieth-yl; ammom'um. bromide... cetylenzyli. methyl-ammon u chloride... eicosyl; trimethyl; ammo ium; romi e. docosyl trimethyl ammonium iodide. oe LhenZyL treated with the quaternary; ammonium salts.

dimethyl ammonium. chloride, octadecyl tri- Density Readings Wave- Film i,% m Treat- Color Former I Color EormerII gf m 1 microns j Nonev I V -A B 0 DE None Ai s- 11121). E Nonc E,

400: .82 .22. .14 .25 .18 .20 .84 .26. .24 .27 .26 .28 .85 .86. 440' .70 .60 .54 .68 .56 .60' .54 .48 .46 .49. .50 .50 1 .21 .22 450 .72 .68 4 .55 .68 .58 .51: .52 .48 .45. .47. .51 .51 .17; .17 460 .70 .51 .54 .67 .55 .59 .50 .44 .44v .45 .47 .47 .13 .13. 500 1.20 1.20- 1.15 1.28 1.13 1.19 1.01 1.01 1.00 .97'100 1.02 .07 1 .07 530 1.49 1.48 r144.- '1.58. 1.48 1.48 1.51 1.48 1.45 1.48 1.52 1.50.. .10 .09 540 1.51 1.48 1.44 1.54. 1.49 1.49. 1.56 1.51 1.47 1.54 1.57 1.58. .12 .11. 550' 1.50 1.43 1.38 1.50 1:45 1.46 1.57 1.49 1.48 1.54 1.53 1.49 .19 .15 000. 1 .85. .68 .56 .76 .50' .59. .78 .58 .491 .71 .55 .54. .85." .65. 650 .84 .24 .14 .26 .19 .28 a .28 .17 .15 .21 .17 .17 1.38 1.33 700 .19' .12 .04 .12 .08 .11 .14 .07 .07 .08 v .08 .10 1.45 1.46

'Taken from the density curves run on the GeneralElectric Company spectrophotometer (described in. the Journal of the Optical Society of .America, vol. 25,.pp. 305-311 (1935)).

Example III and sensitized for green light.

4. A separator layer like. 2.

5. An emulsion layer for color development of a magenta image containin a color former amido acetal of a. polyvinyl alcohol containing several units. of formula I and. containing. a yellow filter dye, e..g., 'Ifartrazinev (Colour Index No. 640) was exposed on a sector wheel sensitometer where each step is double the exposure of the preceding step and through three red, green and blue primary filters and color developed, washed, fixed, washed, bleached, fixed and Washed after the manner described in Example II and then soaked for five minutes in a 0.125% aqueous solution of cetyl dimethyl benzyl ammonium chloride, Washed and dried. The color of the dye image of each layer was changed, most significant was the increase of red and blue light transmission of the magenta layer and the increase of green light transmission of the cyan layer.

In place of the specific quaternary ammonium salts described in the foregoing examples, there may be substituted other specific salts of this type. Thus, there may be employed cetyl trimethyl ammonium bromide. dimethyl dicetyl ammethyl ammonium methosulphate, e yl. tr methyl ammonium. iodida cetyl cyclohexyl. dimethyl ammonium bromide, dodecyl; cyclohexyl dimethylv ammonium bromide, dodecyl; cyclohexyl diethyl ammonium. bromide. dodecyl trime hyl ammonium chloride, cetyl trimethyl ammonium chloride, octyl. trimethyl. ammonium iodide, octadecyltriethy] ammonium bromide, dodecyl trimethyl ammonium bromide, octadecyl benzyl dimethyl ammonium chloride, cetyl' triethanolammom'um. bromide, dodecyl ethanol dimethyl ammonium sulphate, etc.

While the aboveexamples are all directed to the treatment of films of the, type covered; by U. S. Patent No. 2,397,864 the invention, is not limited to such type. Similar films having the color formers of the above patents Which are dispersed in. various water-permeable colloid silver halide emulsions e. a, gelatin, casein,.albumen, and the hydrolyzed ethylene/vinyl. acetate copolymers of U. S..Patent No. 2,397,867 can be similarly treated. Likewise, filmscontaining immobile color formers other than the polyvinyl acetal type can be used. Suitable other color formersv are. immobile containing the carbonamide and sulfonamide groups of the above type are described in. U. S, Patents 2,186,717, 2,356,475, 2,350,138,. 2,319,426, 2,395,484, 2,397,867,. and 2, 5,629.

The invention can be used with elements wherein, the, color formers constitute or are; disposed in a. water permeable. layer or stratum adjacent a light sensitive silver halide layer so that the silver halide grains are in coactive relationship with the color former. Elements of this type are described in U. S. Patents 2,363,764 and 2,350,380.

An advantage of the invention is that it provides an effective process for modifying color developed images in single or multilayer photographic elements. A further advantage is that it provides a simple and economical process for modifying the color of color developed images. A still further advantage is that the process is economical and utilizes commercially available quaternary salts. A further advantage is that it enables the photographic technician to correct the color of a dye image or images.

As many widely different embodiments of this invention can be made Without departing from the spirit and scope thereof, it is to be understood that the invention is not to be limited except as defined by the claims.

Iclaim:

1. In a process of producing a color developed dye image by exposing, color developing by a primary aromatic amine developing agent, bleaching and fixing a photographic film element bearing a light-sensitive silver halide layer having an immobile color former containing an amide group taken from the class consisting of carbonamide and sulfonamide groups which have a hydrogen atom attached to the amido-nitrogen atom in coactive relationship with the silver halide grains; the step which comprises treating the element after exposure in an aqueous treatting bath containing 0.2 gram to 25 grams per liter of a quaternar ammonium salt the positive ion of which contains an aliphatic hydrocarbon radical having a chain of 8 to 22 carbon atoms.

2. In a process of producing a color developed dye image by exposing, color developing by a primary aromatic amine developing agent, fixing, bleaching and fixing a photographic film element bearing a light-sensitive silver halide layer having an immobile color former containing an amide group taken from the class consisting of carbonamide and sulfonamide groups which have a hydrogen atom attached to the amido-nitrogen atom in coactive relationship with the silver halide grains; the step which comprises treating the element after exposure in an aqueous treating bath containing from 0.2 gram to 25 grams per liter of a quaternary ammonium salt, the positive ion of which contains an alkyl radical having from 12 to 18 carbon atoms in a straight chain.

3. In a process of producing a color developed dye image by exposing, color developing by a primary aromatic amine developing agent, fixing, bleaching and fixing a photographic film element bearing a light-sensitive silver halide layer having an immobile polyvinyl acetal color former containing a primary carbonamide group which has a hydrogen atom attached to the amido-nitrogen atom in coactive relationship with the silver halide grains; the step which comprises treating the element after exposure in an aqueous treating bath containing from 0.2 gram to 25.0 grams per liter of a quaternary ammonium salt the positive ion of which contains an aliphatic hydrocarbon radical having a chain of 8 to 22 carbon atoms.

4. In a process of producing a color developed dye image by exposing, color developing by a primary aromatic amine developing agent, fixing, bleaching and fixing a photographic film element bearing a light-sensitive silver halide layer having an immobile polyvinyl acetal color former containing a sulfonamide group which has a hydrogen atom attached to the amidonitrogen atom in coactive relationship with the silver halide grains; the step which comprises treating the element after exposure in an aqueous treating bath containing from 0.2 gram to 25.0 grams per liter of a quaternary ammonium salt the positive ion of which contains an aliphatic hydrocarbon radical having a chain of 8 to 22 carbon atoms.

5. In a process of producing a color developed dye image by exposing, color developing by a primary aromatic amine developing agent, fixing, bleaching and fixing a photographic film element bearing a light-sensitive silver halide layer having an immobile color former containing an amide group taken from the class consistin of carbonamide and sulfonamide groups which have a hydrogen atom attached to the amido-nitrogen atom in coactive relationship with the silver halide grains; the step which comprises developing the exposed element in an aqueous alkaline developing bath containing a primary aromatic amino developing agent and from 0.2 gram to 25.0 grams per liter of a quaternary ammonium salt, the positive ion of which contains an aliphatic hydrocarbon radical having a chain of 8 to 22 carbon atoms.

6. In a process of producing a color developed dye image by exposing, color developing by a primary aromatic amine developing agent, fixing, bleaching and fixing a photographic film element bearing a light-sensitive silver halide layer having an immobile color former containing an amide group taken from the class consisting of carbonamide and sulfonamide groups which have a hydrogen atom attached to the amido-nitrogen atom in coactive relationship with the silver halide grains; the step which comprises treatin the element after fixing in an aqueous treating bath containing from 0.2 gram to 25.0 grams per liter of a quaternary ammonium salt the positive ion of which contains an aliphatic hydrocarbon radical having a chain of 8 to 22 carbon atoms.

VERNON WILLIAM BLANCHARD.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,301,381 Dickey Nov. 10, 1942 2,307,161 Schneider Jan. 5, 1943 2.376.141 I-Ienn May 15, 1945 

1. IN A PROCESS OF PRODUCING A COLOR DEVELOPED DYE IMAGE EXPOSING, COLOR DEVELOPING BY A PRIMARY AROMATIC AMINE DEVELOPING AGENT, BLEACHING AND FIXING A PHOTOGRAPHIC FILM ELEMENT BEARING A LIGHT-SENSITIVE SILVER HALIDE LAYER HAVING AN IMMOBILE COLOR FORMER CONTAINING AN AMIDE GROUP TAKEN FROM THE CLASS CONSISTING OF CARBONAMIDE AND SULFONAMIDE GROUPS WHICH HAVE A HYDROGEN ATOM ATTACHED TO THE AMIDO-NITROGEN ATOM IN COACTIVE RELATIONSHIP WITH THE SILVER HALIDE GRAINS; THE STEP WHICH COMPRISES TREATING THE ELEMENT AFTER EXPOSURE IN AN AQUEOUS TREATTING BATH CONTAINING 0.2 GRAM TO 25 GRAMS PER LITER OF A QUATERNARY AMMONIUM SALT THE POSITIVE ION OF WHICH CONTAINS AN ALIPHATIC HYDROCARBON RADICAL HAVING A CHAIN OF 8 TO 22 CARBON ATOMS. 